Fuel compositions comprising hydantoin-containing polyether alcohol additives

ABSTRACT

The present invention is directed to the use of hydantoin-containing polyether alcohols as additives in a gasoline composition. The invention is also directed to the use of these compounds for decreasing intake valve deposits, controlling octane requirement increases and reducing octane requirement. The invention is further directed to hydantoin-containing compounds.

This is a continuation of application Ser. No. 08/447,368, filed May 23,1995, now abandoned which is a division of application Ser. No.08/308,712, filed Sep. 19, 1994 now U.S. Pat. No. 5,489,315.

FIELD OF THE INVENTION

The present invention relates to the use of hydantoin-containingpolyether alcohol compounds as additives in fuel compositions and theuse of those compounds to decrease intake octane requirement. Thepresent invention further relates to two classes of hydantoin-containingpolyether alcohol compounds.

BACKGROUND OF THE INVENTION

The accumulation of deposits on the intake valves of internal combustionengines presents a variety of problems. The accumulation of suchdeposits is characterized by overall poor driveability including hardstarting, stalls, and stumbles during acceleration and rough engineidle.

Many additives are known which can be added to hydrocarbon fuels toprevent or reduce deposit formation, or remove or modify formeddeposits, in the combustion chamber and on adjacent surfaces such asintake valves, ports, and spark plugs. Continued improvements in thedesign of internal combustion engines, e.g., fuel injection andcarburetor engines, bring changes to the environment of such enginesthereby creating a continuing need for new additives to control theproblem of inlet system deposits and to improve driveability which canbe related to deposits.

It would be an advantage to have fuel compositions which would reducethe formation of deposits and modify existing deposits that are relatedto octane requirement increase and poor driveability in modern engineswhich burn hydrocarbon fuels.

SUMMARY OF THE INVENTION

The present invention is directed to the use of hydantoin-containingpolyether alcohols as additives in fuel compositions comprising a majoramount of a mixture of hydrocarbons in the gasoline boiling range and aminor amount of one or more hydantoin-containing polyether alcoholcompounds of Formula I: ##STR1## wherein R₁ is selected from the groupconsisting of hydrocarbyl of 1 to 100 carbon atoms, substitutedhydrocarbyl of 1 to 100 carbon atoms and polyoxyalkylene alcohol of 2 to200 carbon atoms; R₂ and R₃ are each independently selected from thegroup consisting of hydrogen, hydrocarbyl of 1 to 100 carbon atoms andsubstituted hydrocarbyl of 1 to 100 carbon or R₂ and R₃ taken togetherwith the carbon atom to which they are connected form a cyclic group of4 to 100 carbon atoms; each R₄ is independently selected from the groupconsisting of hydrocarbyl of 2 to 100 carbon atoms and substitutedhydrocarbyl of 2 to 100 carbon atoms; and x is from 1 to 50;

or a minor amount of one or more of the hydantoin-containing polyetheralcohol compounds of Formula II: ##STR2## wherein R₁ and R₇ are eachindependently selected from the group consisting of hydrocarbyl of 1 to100 carbon atoms, substituted hydrocarbyl of 1 to 100 carbon atoms andpolyoxyalkylene alcohol of 2 to 200 carbon atoms; R₆ is selected fromthe group consisting of hydrogen, hydrocarbyl of 1 to 100 carbon atoms,substituted hydrocarbyl of 1 to 100 carbon atoms and polyoxyalkyl offormula:

    --O--R.sub.10                                              (III)

wherein R₁₀ is selected from the group consisting of hydrocarbyl of 1 to100 carbon atoms, substituted hydrocarbyl of 1 to 100 carbon atoms andpolyoxyalkylene alcohol of 2 to 200 carbon atoms with the proviso thatwhen both R₁ and R₇ are not polyoxyalkylene alcohol, R₆ must bepolyoxyalkyl wherein R₁₀ is polyoxyalkylene alcohol of 2 to 200 carbonatoms; R₅ is selected from the group consisting of hydrocarbyl of 1 to100 carbon atoms and substituted hydrocarbyl of 1 to 100 carbon atoms;R₂, R₃, R₈ and R₉ are each independently selected from the groupconsisting of hydrogen, hydrocarbyl of 1 to 100 carbon atoms andsubstituted hydrocarbyl of 1 to 100 carbon atoms or R₂ and R₃ and/or R₈and R₉ can each independently be taken together with the carbon atom towhich they are connected to form a cyclic group of 4 to 100 carbonatoms.

The invention is also directed to the use of these hydantoin-containingpolyether alcohols for decreasing intake valve deposits, controllingoctane requirement increases and reducing octane requirement. Theinvention is further directed to two classes of hydantoin-containingpolyether alcohol compounds.

DESCRIPTION OF THE PREFERRED EMBODIMENTS COMPOUNDS

The compounds of the present invention, broadly expressed ashydantoin-containing polyether alcohols, are new additives useful forhydrocarbon fuels, e.g., fuels in the gasoline boiling range, forpreventing deposits in engines. These compounds are also proposed forcontrolling octane requirement increases and reducing octanerequirement. The compounds produce very little residue and are misciblewith carriers and other detergents. Non-limiting illustrativeembodiments of the compounds useful as additives in the instantinvention include those of Formula I: ##STR3##

In Formula I, R₁ is selected from the group consisting of hydrocarbyl of1 to 100 carbon atoms, substituted hydrocarbyl of 1 to 100 carbon atomsand polyoxyalkylene alcohol of 2 to 200 carbon atoms.

As used herein, the term "hydrocarbyl" represents a radical formed bythe removal of one or more hydrogen atoms from a carbon atom of ahydrocarbon (not necessarily the same carbon atom). Useful hydrocarbylsare aliphatic, aromatic, substituted, unsubstituted, acyclic or cyclic.Preferably, the hydrocarbyls are aryl, alkyl, alkenyl or cycloalkyl andare straight-chain or branched-chain. Representative hydrocarbylsinclude methyl, ethyl, butyl, pentyl, methylpentyl, hexenyl, ethylhexyl,dimethylhexyl, octamethylene, octenylene, cyclooctylene,methylcyclooctylene, dimethylcyclooctyl, isooctyl, dodecyl, hexadecenyl,octyl, eicosyl, hexacosyl, triacontyl and phenylethyl. As noted, thehydrocarbyls utilized may be substituted. As used herein, the term"substituted hydrocarbyl" refers to any "hydrocarbyl" which contains afunctional group such as carbonyl, carboxyl, nitro, amino, hydroxy (e.g.hydroxyethyl), oxy, cyano, sulfonyl, and sulfoxyl. The majority of theatoms, other than hydrogen, in substituted hydrocarbyls are carbon, withthe heteroatoms (i.e., oxygen, nitrogen, sulfur) representing only aminority, 33% or less, of the total non-hydrogen atoms present.

When R₁ is hydrocarbyl or substituted hydrocarbyl, R₁ is preferablyselected from hydrocarbyl of 1 to 50 carbon atoms and substitutedhydrocarbyl of 1 to 50 carbon atoms. In the more preferred embodiments,R₁ is hydrocarbyl. Preferably when R₁ is hydrocarbyl, it is hydrocarbylselected from alkyl of 1 to 20 carbon atoms, cyclic alkyl of 4 to 20carbon atoms and aromatic of 6 to 20 carbon atoms, more preferably alkylof 1 to 10 carbon atoms, cyclic alkyl of 5 to 10 carbon atoms andaromatic of 6 to 10 carbon atoms and most preferably alkyl of 1 to 5carbon atoms, cyclic alkyl of 5 to 8 carbon atoms and aromatic of 6carbon atoms. In the most preferred embodiments, when R₁ is hydrocarbyl,it is selected from alkyl of 1 to 20 carbon atoms and more preferablyalkyl of 1 to 10 carbon atoms, especially methyl. When R₁ is hydrocarbylof a relatively high number of carbon atoms, i.e., greater than about 50carbon atoms, R₁ will be represented by polymeric hydrocarbyls derivedfrom polyisobutylene, polybutene, polypropylene or polyalphaolefins.

When R₁ is polyoxyalkylene alcohol of 2 to 200 carbon atoms, R₁ ispreferably polyoxyalkylene alcohol of Formula IV:

    --(R.sub.11 --O).sub.y H                                   (IV)

wherein each R₁₁ is independently selected from the group consisting ofhydrocarbyl, as defined hereinbefore, of 2 to 100 carbon atoms andsubstituted hydrocarbyl, as defined hereinbefore, of 2 to 100 carbonatoms and y is from 1 to 50. Preferably, each R₁₁ is independentlyselected from hydrocarbyl of 2 to 100 carbon atoms. When R₁₁ ishydrocarbyl of a relatively high number of carbon atoms, i.e., greaterthan about 50 carbon atoms, each will be represented by polymerichydrocarbyls derived from polyisobutylene, polybutene, polypropylene orpoly-alphaolefins. More preferably, each R₁₁ is independently selectedfrom hydrocarbyl of 2 to 20 carbon atoms. Particularly preferredcompounds are those in which each R₁₁ is independently selected fromalkyl of 2 to 20 carbon atoms, more preferably alkyl of 2 to 4 carbonatoms, especially alkyl of 4 carbon atoms.

Particularly preferred compounds of Formula I are those in which when R₁is polyoxyalkylene alcohol, R₁₁ is hydrocarbyl (geminal or vicinal) ofFormula V or Formula VI: ##STR4## wherein R₁₂, R₁₃ and R₁₄ are eachindependently selected from hydrogen, hydrocarbyl, as definedhereinbefore, of 1 to 98 carbon atoms and substituted hydrocarbyl, asdefined hereinbefore, of 1 to 98 carbon atoms. Preferably R₁₂, R₁₃ andR₁₄ are independently selected from hydrogen, hydrocarbyl of 1 to 18carbon atoms and substituted hydrocarbyl of 1 to 18 carbon atoms. R₁₃and R₁₂, or in the alternative R₁₂ and R₁₄, may be taken together toform a divalent linking hydrocarbyl group of 3 to 12 carbon atoms.

The most preferred compounds of Formula I are those in which when R₁ ispolyoxyalkylene, R₁₁ is hydrocarbyl as represented by Formula V abovewherein each R₁₄ is hydrogen and each R₁₂ is independently selected fromhydrogen, alkyl of 1 to 18 carbon atoms and oxy-substituted hydrocarbylof 1 to 18 carbon atoms, particularly those compounds where each R₁₄ ishydrogen and each R₁₂ is independently hydrogen or alkyl of 1 to 2carbon atoms, especially those compounds where each R₁₄ is hydrogen andeach R₁₂ is alkyl of two carbon atoms.

When R₁₂ is oxy-substituted hydrocarbyl of 1 to 18 carbon atoms, R₁₂ ispreferably an alkoxy-substituted alkylene of 1 to 18 carbon atoms or anaryloxy-substituted alkylene of 1 to 18 carbon atoms. Particularlypreferred alkoxy-substituted alkylene groups includeethylhexyleneoxymethylene, isopropoxymethylene, butoxymethylene andmixtures thereof. Particularly preferred aryl-substituted alkylenegroups include nonylphenoxymethylene, phenoxymethylene and mixturesthereof.

In Formula IV above, y is from 1 to 50, preferably from 1 to 40, andeven more preferably from 1 to 26. Those of ordinary skill in the artwill recognize that when the compounds of Formula I which contain thepolyoxyalkylene alcohol of Formula IV are used in a composition, y willnot have a fixed value but will instead be represented by a range ofdifferent values. As used in this specification, y is considered to be a(number) average of the various values of y that are found in a givencomposition, which number has been rounded to the nearest integer. Therange of y was determined by gel permeation chromatography (GPC)analysis in the various examples and is indicated in the variousexamples by the polydispersity (polydispersity=molecular weight based onthe weight average divided by the molecular weight based on the numberaverage).

When y is greater than 1, the individual R₁₁ 's are the same ordifferent. For example, if y is 20, each R₁₁ can be alkyl of four carbonatoms. Alternatively, the R₁₁ 's can differ and for instance,independently be alkyl from two to four carbon atoms. When the R₁₁ 'sdiffer, they may be present in blocks, i.e., all y groups in which R₁₁is alkyl of three carbon atoms will be adjacent, followed by all ygroups in which R₁₁ is alkyl of two carbon atoms, followed by all ygroups in which R₁₁ is alkyl of four carbon atoms. When the R₁₁ 'sdiffer, they may also be present in any random distribution.

In an alternative preferred embodiment of the present invention, R₁ willbe polyoxyalkylene alcohol of Formula IV as defined hereinbefore. WhenR₁ is polyoxyalkylene alcohol of Formula IV, preferably the sum of thevalues of x and y will not exceed 40, more preferably the sum of thevalues of x and y will not exceed 26. In the most preferred embodimentof when R₁ is polyoxyalkylene alcohol of Formula IV, x will be from 1 to13 and y will be from 1 to 13.

R₂ and R₃ are each independently selected from the group consisting ofhydrogen, hydrocarbyl, as defined hereinbefore, of 1 to 100 carbon atomsand substituted hydrocarbyl, as defined hereinbefore, of 1 to 100 carbonatoms or R₂ and R₃ taken together with the carbon atom to which they areconnected form a cyclic group of 4 to 100 carbon atoms. When R₂ and/orR₃ are hydrocarbyl or substituted hydrocarbyl, each R₂ and/or R₃ arepreferably independently selected from hydrocarbyl of 1 to 50 carbonatoms and substituted hydrocarbyl of 1 to 50 carbon atoms. Morepreferably, R₂ and/or R₃ are independently selected from hydrocarbyl of1 to 20 carbon atoms. Preferably R₂ and/or R₃ are each independentlyselected from hydrocarbyl comprising alkyl of 1 to 20 carbon atoms,cyclic alkyl of 4 to 20 carbon atoms and aromatic of 6 to 20 carbonatoms, more preferably alkyl of 1 to 10 carbon atoms, cyclic alkyl of 5to 10 carbon atoms and aromatic of 6 to 10 carbon atoms and mostpreferably alkyl of 1 to 5 carbon atoms, cyclic alkyl of 5 to 8 carbonatoms and aromatic of 6 carbon atoms. In the most preferred embodiments,when R₂ and/or R₃ are hydrocarbyl, each is selected from alkyl of 1 to20 carbon atoms and more preferably alkyl of 1 to 10 carbon atoms, mostpreferably methyl. R₂ and R₃ may be the same or different. In the mostpreferred embodiments, R₂ and R₃ will be the same.

When R₂ and/or R₃ are hydrocarbyl of a relatively high number of carbonatoms, i.e., greater than about 50 carbon atoms, R₂ and/or R₃ will berepresented by polymeric hydrocarbyls derived from polyisobutylene,polybutene, polypropylene or poly-alphaolefin.

R₂ and R₃ can also be taken together with the carbon atom to which theyare attached to form a cyclic group of 4 to 100 carbon atoms. As usedherein, the term "cyclic group" refers to when R₂ and R₃ together withthe carbon atom to which they are connected form an alicyclic ring or anarene. Note that for purposes of calculating the number of carbon atomsin the cyclic group when R₂ and R₃ are taken together to form a cyclicgroup, the carbon atom to which R₂ and R₃ are connected is included.Preferably when R₂ and R₃ are taken together with the carbon atom towhich they are connected, they form a cyclic group of 5 to 50 carbonatoms, even more preferably of 5 to 20 carbon atoms and most preferably5 to 8 carbon atoms.

As noted, when R₂ and R₃ taken together with the carbon atom to whichthey are connected form a "cyclic group", they will be a partialstructure in the form of a ring which is alicyclic or arene. When R₂ andR₃ taken together form an alicyclic ring, the ring can be cycloalkyl orcycloalkenyl (i.e., cyclohexyl, cyclopentyl, cyclododecyl, cyclooctyl,cyclohexenyl or cyclopentyl). In addition, the ring may be bicyclic(i.e., bicycloalkyl or bicycloalkenyl) or fused to additional ringstructures to form polycyclic or multiple ring groups (i.e., norbonyl orbicyclo(3,3,1)nonyl). A variety of substituents such as one or morealkyl or aryl groups may also be present on any one or more of the rings(i.e., 2-methylcyclopentyl or 4-butylcyclohexyl). When substituents arepresent, they can be in a variety of forms, including but not limited tostraight or branched chained alkyls. In addition, R₂ and R₃ can be takentogether with the carbon atom to which they are connected to form anarene such as 9-fluorenyl. R₂ and R₃ can also be taken together with thecarbon atom to which they are connected to form a "substituted cyclicgroup" which refers to any "cyclic group" which has a substituentattached to the cyclic group and the substituent includes a functionalgroup such as carbonyl, carboxyl, nitro, amino, hydroxy, oxy, cyano,sulfonyl or sulfoxyl.

When R₂ and R₃ together form a cyclic group, they will preferably form acycloalkyl or a bicycloalkyl of 5 to 50 carbon atoms, with cyclohexylbeing the most preferred cycloalkyl and benzene derivatives andnaphthalene derivatives being the most preferred bicycloalkyls.

Representative examples of R₂ and R₃ taken together to form cyclicgroups are illustrated by the following partial structures: cycloalkylssuch as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl; substitutedcycloalkyls such as methylcyclohexyl, ethylcyclohexyl, andbutylcyclohexyl; bicycloalkyls such as bicyclo 2,2,1!heptyl, bicyclo2,2,2!octyl and bicyclo 4,2,2!decyl; substituted bicycloalkyls such asmethyl-bicyclo 2,2,1!heptyl and methyl-bicyclo 2,2,21!octyl; multiplerings such as benzocyclohexyl and benzocyclopentyl; substituted multiplerings which are derivatives from the Diels-Alder of dicyclopentadiene;and arenes such as 9-fluoroenyl.

Each R₄ is independently selected from the group consisting ofhydrocarbyl, as defined hereinbefore, of 2 to 100 carbon atoms, orsubstituted hydrocarbyl, as defined hereinbefore, of 2 to 100 carbonatoms. Preferably each R₄ is independently hydrocarbyl or substitutedhydrocarbyl of 2 to 50 carbon atoms, more preferably of 2 to 20 carbonatoms. The most preferred compounds are those in which each R₄ isindependently selected from hydrocarbyl of 2 to 4 carbon atoms. When R₄is hydrocarbyl of a relatively high number of carbon atoms, i.e.,greater than about 50 carbon atoms, R₄ will be represented by polymerichydrocarbyls derived from polyisobutylene, polybutene, polypropylene orpoly-alphaolefins.

Particularly preferred compounds of Formula I are those in which R₄ ishydrocarbyl (geminal or vicinal) of Formula VII or Formula VIII:##STR5## wherein R₁₅, R₁₆ and R₁₇ are each independently selected fromhydrogen, hydrocarbyl, as defined hereinbefore, of 1 to 98 carbon atomsand substituted hydrocarbyl, as defined hereinbefore, of 1 to 98 carbonatoms. Preferably R₁₅, R₁₆ and R₁₇ are each independently selected fromhydrogen, hydrocarbyl of 1 to 18 carbon atoms and substitutedhydrocarbyl of 1 to 18 carbon atoms. R₁₆ and R₁₅, or in the alternativeR₁₅ and R₁₇, may be taken together to form a divalent linkinghydrocarbyl group of 3 to 12 carbon atoms.

The most preferred compounds of Formula I are those in which R₄ ishydrocarbyl as represented by Formula VII above wherein each R₁₇ ishydrogen and each R₁₅ is independently selected from hydrogen, alkyl of1 to 18 carbon atoms and oxysubstituted hydrocarbyl of 1 to 18 carbonatoms, particularly those compounds where each R₁₇ is hydrogen and eachR₁₅ is independently selected from hydrogen and alkyl of 1 to 2 carbonatoms, especially those compounds where each R₁₇ is hydrogen and eachR₁₅ is alkyl of two carbon atoms.

When R₁₅ is oxy-substituted hydrocarbyl of 1 to 18 carbon atoms, R₁₅ ispreferably an alkoxy-substituted alkylene of 1 to 18 carbon atoms or anaryloxy-substituted alkylene of 1 to 18 carbon atoms. Particularlypreferred alkoxy-substituted alkylene groups includeethylhexyleneoxymethylene, isopropoxymethylene, butoxymethylene andmixtures thereof. Particularly preferred aryl-substituted alkylenegroups include nonylphenoxymethylene, phenoxymethylene and mixturesthereof.

In Formula I above, x is from 1 to 50, preferably from 1 to 40, and evenmore preferably from 1 to 26. Those of ordinary skill in the art willrecognize that when the compounds of Formula I are used in acomposition, x will not have a fixed value but will instead berepresented by a range of different values. As used in thisspecification, x is considered to be a (number) average of the variousvalues of x that are found in a given composition, which number has beenrounded to the nearest integer. The range of x was determined by gelpermeation chromatography (GPC) analysis in the various examples and isindicated in the various examples by the polydispersity(polydispersity=molecular weight based on the weight average divided bythe molecular weight based on the number average). The same isapplicable with regard to y of Formula IV.

When x is greater than 1, the individual R₄ 's are the same ordifferent. For example, if x is 20, each R₄ can be alkyl of four carbonatoms. Alternatively, the R₄ 's can differ and for instance,independently be alkyl from two to four carbon atoms. When the R₄ 'sdiffer, they may be present in blocks, i.e., all x groups in which R₄ isalkyl of three carbon atoms will be adjacent, followed by all x groupsin which R₄ is alkyl of two carbon atoms, followed by all x groups inwhich R₄ is alkyl of four carbon atoms. When the R₄ 's differ, they mayalso be present in any random distribution.

In one preferred embodiment of the present invention, R₁ is selectedfrom hydrocarbyl of 1 to 100 carbon atoms, preferably alkyl of 1 to 20carbon atoms and even more preferably methyl. In the preferredembodiment when R₁ is selected from hydrocarbyl of 1 to 100 carbonatoms, x will preferably range from 8 to 26.

The present invention is also directed to compounds of Formula I whereinR₁, R₂, R₃, R₄ and x are as defined hereinbefore.

The compounds of Formula I have a weight average molecular weight of atleast 600. Preferably, the weight average molecular weight is from about800 to about 4000, even more preferably from about 800 to about 2000.

Typical compounds represented by Formula I and the correspondinginitiators used to make these compounds include those listed bystructure in Table I.

                                      TABLE I                                     __________________________________________________________________________    Initiator       Product                                                       __________________________________________________________________________     ##STR6##                                                                                      ##STR7##                                                                     wherein x is from 1 to 26 and y is from 1 to 26.               ##STR8##                                                                                      ##STR9##                                                                     wherein x is from 8 to 26.                                    __________________________________________________________________________

Additional non-limiting illustrative embodiments of the compounds usefulas additives in the instant invention also include those of Formula II:##STR10##

In Formula II, R₁ and R₇ are each independently selected from the groupconsisting of hydrocarbyl, as defined hereinbefore, of 1 to 100 carbonatoms, substituted hydrocarbyl, as defined hereinbefore, of 1 to 100carbon atoms and polyoxyalkylene alcohol of 2 to 200 carbon atoms. R₁and R₇ may be the same or different. In the most preferred embodiments,R₁ and R₇ are the same.

When R₁ and/or R₇ are hydrocarbyl or substituted hydrocarbyl, R₁ and/orR₇ are preferably selected from hydrocarbyl of 1 to 50 carbon atoms orsubstituted hydrocarbyl of 1 to 50 carbon atoms. Preferably, R₁ and/orR₇ are hydrocarbyl. Preferably when R₁ and/or R₇ are hydrocarbyl, theyare hydrocarbyl independently selected from alkyl of 1 to 20 carbonatoms, cyclic alkyl of 4 to 20 carbon atoms and aromatic of 6 to 20carbon atoms, more preferably alkyl of 1 to 10 carbon atoms, cyclicalkyl of 5 to 10 carbon atoms and aromatic of 6 to 10 carbon atoms andmost preferably alkyl of 1 to 5 carbon atoms, cyclic alkyl of 5 to 8carbon atoms and aromatic of 6 carbon atoms. In the more preferredembodiments, R₁ and/or R₇ are each independently hydrocarbyl selectedfrom alkyl of 1 to 20 carbon atoms, more preferably alkyl of 1 to 10carbon atoms and most preferably alkyl of 1 to 5 carbon atoms.

When R₁ and/or R₇ are hydrocarbyl of a relatively high number of carbonatoms, i.e., greater than about 50 carbon atoms, R₁ and/or R₇ will bepolymeric hydrocarbyls derived from polyisobutylene, polybutene,polypropylene or poly-alphaolefin.

R₆ is selected from the group consisting of hydrogen, hydrocarbyl, asdefined hereinbefore, of 1 to 100 carbon atoms, substituted hydrocarbyl,as defined hereinbefore, of 1 to 100 carbon atoms and polyoxyalkyl ofFormula III:

    --O--R.sub.10                                              (III)

wherein R₁₀ is selected from the group consisting of hydrocarbyl, asdefined hereinbefore, of 1 to 100 carbon atoms, substituted hydrocarbyl,as defined hereinbefore, of 1 to 100 carbon atoms and polyoxyalkylenealcohol of 2 to 200 carbon atoms with the proviso that when both R₁ andR₇ are not polyoxyalkylene alcohol, R₆ must be polyoxyalkyl of FormulaIII wherein --R₁₀ is polyoxyalkylene alcohol of 2 to 200 carbon atoms.

When R₆ is hydrocarbyl or substituted hydrocarbyl, R₆ is preferablyselected from hydrocarbyl of 1 to 50 carbon atoms or substitutedhydrocarbyl of 1 to 50 carbon atoms. More preferably, R₆ is hydrocarbylof 1 to 20 carbon atoms. When R₆ is hydrocarbyl, it is preferablyhydrocarbyl comprising alkyl of 1 to 20 carbon atoms, cyclic alkyl of 4to 20 carbon atoms and aromatic of 6 to 20 carbon atoms, more preferablyalkyl of 1 to 10 carbon atoms, cyclic alkyl of 5 to 10 carbon atoms andaromatic of 6 to 10 carbon atoms, and most preferably alkyl of 1 to 5carbon atoms, cyclic alkyl of 5 to 8 carbon atoms and aromatic of 6carbon atoms. In the more preferred embodiments, when R₆ is hydrocarbyl,it is selected from alkyl of 1 to 20 carbon atoms, more preferably alkylof 1 to 10 carbon atoms, and most preferably alkyl of 1 to 5 carbonatoms.

When R₆ is hydrocarbyl of a relatively high number of carbon atoms,i.e., greater than about 50 carbon atoms, R₆ will be represented bypolymeric hydrocarbyls derived from polyisobutylene, polybutene,polypropylene or poly-alphaolefin.

R₆ can also be polyoxyalkyl. When R₆ is polyoxyalkyl, it will bepolyoxyalkyl of Formula III:

    --O--R.sub.10                                              (III)

wherein R₁₀ is selected from the group consisting of hydrocarbyl, asdefined hereinbefore, of 1 to 100 carbon atoms, substituted hydrocarbyl,as defined hereinbefore, of 1 to 100 carbon atoms and polyoxyalkylenealcohol of 2 to 200 carbon atoms. When R₁₀ is hydrocarbyl or substitutedhydrocarbyl, R₁₀ is preferably hydrocarbyl of 1 to 50 carbon atoms orsubstituted hydrocarbyl of 1 to 50 carbon atoms. More preferably, R₁₀ ishydrocarbyl of 1 to 20 carbon atoms, even more preferably, alkyl of 1 to20 carbon atoms, and most preferably alkyl of 1 to 10 carbon atoms.

When R₁, R₇ and/or R₁₀ are polyoxyalkylene alcohol of 2 to 200 carbonatoms, R₁, R₇ and/or R₁₀ are preferably each polyoxyalkylene alcohol ofFormula IX: ##STR11## wherein each R₁₈ is independently selected fromthe group consisting of hydrocarbyl, as defined hereinbefore, of 2 to100 carbon atoms and substituted hydrocarbyl, as defined hereinbefore,of 2 to 100 carbon atoms and z is from 1 to 50. Preferably, each R₁₈ isindependently selected from hydrocarbyl of 2 to 100 carbon atoms. WhenR₁₈ is hydrocarbyl of a relatively high number of carbon atoms, i.e.,greater than about 50 carbon atoms, each will be represented bypolymeric hydrocarbyls derived from polyisobutylene, polybutene,polypropylene or poly-alphaolefin. More preferably, each R₁₈ isindependently selected from hydrocarbyl of 2 to 20 carbon atoms.Particularly preferred compounds are those in which each R₁₈ isindependently alkyl of 2 to 20 carbon atoms, more preferably alkyl of 2to 4 carbon atoms, especially alkyl of 4 carbon atoms.

Particularly preferred compounds of Formula II are those in which whenR₁, R₇ and/or R₁₀ are polyoxyalkylene alcohol of Formula IX, R₁₈ ishydrocarbyl (geminal or vicinal) of Formula X or Formula XI: ##STR12##wherein R₁₉, R₂₀ and R₂₁, are each independently selected from hydrogen,hydrocarbyl, as defined hereinbefore, of 1 to 98 carbon atoms andsubstituted hydrocarbyl, as defined hereinbefore, of 1 to 98 carbonatoms. Preferably R₁₉, R₂₀ and R₂₁ are each independently selected fromhydrogen, hydrocarbyl of 1 to 18 carbon atoms and substitutedhydrocarbyl of 1 to 18 carbon atoms. R₁₉ and R₂₀, or in the alternativeR₁₉ and R₂₁, may be taken together to form a divalent linkinghydrocarbyl group of 3 to 12 carbon atoms.

The most preferred compounds of Formula II are those in which when R₁,R₇ and/or R₁₀ are polyoxyalkylene alcohol, R₁₈ is hydrocarbyl asrepresented by Formula X above wherein each R₂₁, is hydrogen and eachR₁₉ is independently selected from hydrogen, alkyl of 1 to 18 carbonatoms and oxy-substituted hydrocarbyl of 1 to 18 carbon atoms,particularly those compounds where each R₂₁ is hydrogen and each R₁₉ isindependently selected from hydrogen and alkyl of 1 to 2 carbon atoms,especially those compounds where each R₂₁ is hydrogen and each R₁₉ isalkyl of two carbon atoms.

When R₁₉ is oxy-substituted hydrocarbyl of 1 to 18 carbon atoms, R₁₉ ispreferably an alkoxy-substituted alkylene of 1 to 18 carbon atoms or anaryloxy-substituted alkylene of 1 to 18 carbon atoms. Particularlypreferred alkoxy-substituted alkylene groups includeethylhexyleneoxymethylene, isopropoxymethylene, butoxymethylene andmixtures thereof. Particularly preferred aryl-substituted alkylenegroups include nonylphenoxymethylene, phenoxymethylene and mixturesthereof.

In Formula IX above, z is from 1 to 50, preferably from 1 to 40, andeven more preferably from 1 to 26. When two or more polyoxyalkylenealcohol groups of the Formula IX are present, z will preferably be from1 to 13. Those of ordinary skill in the art will recognize that whencompounds of Formula I which contain the polyoxyalkylene alcohol ofFormula IX are used in a composition, z will not have a fixed value butwill instead be represented by a range of different values. As used inthis specification, z is considered to be a (number) average of thevarious values of z that are found in a given composition, which numberhas been rounded to the nearest integer. The range of z was determinedby gel permeation chromatography (GPC) analysis in the various examplesand is indicated in the various examples by the polydispersity(polydispersity=molecular weight based on the weight average divided bythe molecular weight based on the number average).

When z is greater than 1, the individual R₁₈ 's are the same ordifferent. For example, if z is 20, each R₁₈ can be alkyl of four carbonatoms. Alternatively, the R₁₈ 's can differ and for instance,independently be alkyl from two to four carbon atoms. When the R₁₈ 'sdiffer, they may be present in blocks, i.e., all z groups in which R₁₈is alkyl of three carbon atoms will be adjacent, followed by all zgroups in which R₁₈ is alkyl of two carbon atoms, followed by all zgroups in which R₁₈ is alkyl of four carbon atoms. When the R₁₈ 'sdiffer, they may also be present in any random distribution.

As previously noted, when R₁, and R₇ are not polyoxyalkylene alcohol, R₆must be polyoxyalkyl of Formula III (--O--R₁₀) and R₁₀ must bepolyoxyalkylene alcohol of 2 to 200 carbon atoms. In one embodiment,when R₁ and R₇ are not polyoxyalkylene alcohol and R₆ is polyoxyalkyl ofFormula II wherein R₁₀ is polyoxyalkylene alcohol of Formula IX, z willpreferably range from 8 to 26. In another preferred embodiment, R₁ andR₇ are each polyoxyalkylene alcohol of 2 to 200 carbon atoms and R₆ ispolyoxyalkyl of the formula --O--R₁₀ wherein R₁₀ is polyoxyalkylenealcohol of 2 to 200 carbon atoms. In the preferred embodiment when R₁and R₇ are polyoxyalkylene alcohol of 2 to 200 carbon atoms and R₆ ispolyoxyalkyl of the formula --O--R₁₀ wherein R₁₀ is polyoxyalkylenealcohol of 2 to 200 carbon atoms, the sum of the values of all three z'swill preferably not exceed 40 and even more preferably the sum of thevalues of all three z's will not exceed 26. In a still alternativepreferred embodiment, R₁ and R₇ are each independently polyoxyalkylenealcohol of 2 to 200 carbon atoms and R₆ is hydrogen or alkyl of 1 to 10carbon atoms. In the preferred embodiment when R₁ and R₇ are eachindependently polyoxyalkylene alcohol of 2 to 200 carbon atoms and R₆ ishydrogen or alkyl of 1 to 10 carbon atoms, the sum of the values of bothz's will preferably not exceed 40, even more preferably, the sum of thevalues of both z's will not exceed 26.

R₅ is selected from the group consisting of hydrocarbyl, as definedhereinbefore, of 1 to 100 carbon atoms and substituted hydrocarbyl, asdefined hereinbefore, of 1 to 100 carbon atoms. Preferably, R₅ ishydrocarbyl or substituted hydrocarbyl of 1 to 50 carbon atoms and evenmore preferably of 1 to 20 carbon atoms. In the more preferredembodiments, R₅ is hydrocarbyl comprising alkylene of 1 to 20 carbonatoms, even more preferably alkylene of 1 to 10 carbon atoms and mostpreferably alkylene of 1 to 3 carbon atoms.

R₂, R₃, R₈ and R₉ are each independently selected from the groupconsisting of hydrogen, hydrocarbyl, as defined hereinbefore, of 1 to100 carbon atoms and substituted hydrocarbyl, as defined hereinbefore,of 1 to 100 carbon atoms. In the alternative, R₂ and R₃ taken togetherwith the carbon atom to which they are connected form a cyclic group of4 to 100 carbon atoms or R₈ and R₉ taken together with the carbon atomto which they are connected form a cyclic group of 4 to 100 carbonatoms. In one embodiment, R₂ and R₃ taken together form a cyclic groupof 4 to 100 carbon atoms and R₈ and R₉ taken together form a cyclicgroup of 4 to 100 carbon atoms. In an additional embodiment, only one ofthe two groups (R₂ and R₃ or R₈ and R₉) form a cyclic group of 4 to 100carbon atoms.

When R₂, R₃, R₈ and/or R₉ are hydrocarbyl or substituted hydrocarbyl,R₂, R₃, R₈ and/or R₉ are preferably each independently selected fromhydrocarbyl of 1 to 50 carbon atoms or substituted hydrocarbyl of 1 to50 carbon atoms. More preferably, R₂, R₃, R₈ and/or R₉ are eachindependently selected from hydrocarbyl of 1 to 20 carbon atoms.Preferably R₂, R₃, R₈ and/or R₉ are each independently selected fromhydrocarbyl comprising alkyl of 1 to 20 carbon atoms, cyclic alkyl of 1to 20 carbon atoms and aromatic of 1 to 20 carbon atoms. In the mostpreferred embodiments, when R₂, R₃, R₈ and/or R₉ are hydrocarbyl orsubstituted hydrocarbyl, each is independently selected from alkyl of 1to 20 carbon atoms, more preferably alkyl of 1 to 10 carbon atoms andmost preferably alkyl of 1 carbon atom. R₂, R₃, R₈ and R₉ may be thesame or different. In the most preferred embodiments, they are all thesame.

When R₂, R₃, R₈ and/or R₉ are hydrocarbyl of a relatively high number ofcarbon atoms, i.e., greater than about 50 carbon atoms, R₂, R₃, R₈and/or R₉ will each independently be represented by polymerichydrocarbyls derived from polyisobutylene, polybutene, polypropylene orpoly-alphaolefins.

As noted, R₂ and R₃ taken together with the carbon atom to which theyare connected can form a cyclic group of 4 to 100 carbon atoms. Inaddition, R₈ and R₉ taken together with the carbon atom to which theyare connected can form a cyclic group of 4 to 100 carbon atoms. As usedherein, the term "cyclic group" refers to when R₂ and R₃ and/or R₈ andR₉ are taken together with the carbon atom to which they are connectedto form an alicyclic ring or an arene. Note that for purposes ofcalculating the number of carbon atoms in the cyclic group when R₂ andR₃ are taken together to form a cyclic group the carbon atom to whichthey are connected is included. The same applies with regard to when R₈and R₉ are taken together to form a cyclic group. Preferably when R₂ andR₃ and/or R₈ and R₉ are taken together, they form a cyclic group of 5 to50 carbon atoms, even more preferably of 5 to 20 carbon atoms and mostpreferably 5 to 8 carbon atoms.

As noted, when R₂ and R₃ and/or R₈ and R₉ taken together form a "cyclicgroup", they will be a partial structure in the form of a ring whichwill be alicyclic or arene. When R₂ and R₃ and/or R₈ and R₉ takentogether form an alicyclic ring, the ring can be cycloalkyl orcycloalkenyl (i.e., cyclohexyl, cyclopentyl, cyclododecyl, cyclooctyl,cyclohexenyl or cyclopentyl). In addition, the ring may be bicyclic(i.e., bicycloalkyl or bicycloalkenyl) or fused to additional ringstructures to form polycyclic or multiple ring groups (i.e., norbonyl orbicyclo(3,3,1)nonyl). A variety of substituents such as one or morealkyl groups or aryl groups may also be present on any one or more ofthe rings (i.e., 2-methylcyclopentyl or 4-butylcyclohexyl). Whensubstituents are present, they can be in a variety of forms, includingbut not limited to straight or branched chained alkyls. In addition, R₂and R₃ and/or R₈ and R₉ can be taken together with the carbon atom towhich they are connected to form an arene such as 9-fluorenyl. R₂ and R₃and/or R₈ and R₉ can also be taken together to form a "substitutedcyclic group" which refers to any "cyclic group" which has a substituentattached to the cyclic group and the substituent includes a functionalgroup such as carbonyl, carboxyl, nitro, amino, hydroxy, oxy, cyano,sulfonyl or sulfoxyl.

When R₂ and R₃ and/or R₈ and R₉ together form a cyclic group, they willpreferably form a cycloalkyl or a bicycloalkyl of 5 to 20 carbon atoms,with cyclohexyl being the most preferred cycloalkyl and benzenederivatives and naphthalene derivatives being the most preferredbicycloalkyls.

Representative examples of R₂ and R₃ and/or R₈ and R₉ taken together toform cyclic groups are illustrated by the following partial structures:cycloalkyls such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl;substituted cycloalkyls such as methylcyclohexyl, ethylcyclohexyl, andbutylcyclohexyl; bicycloalkyls such as bicyclo 2,2,1!heptyl, bicyclo2,2,21!octyl and bicyclo 4,2,2!decyl; substituted bicycloalkyls such asmethyl-bicyclo 2,2,1!heptyl and methyl-bicyclo 2,2,2!octyl; multiplerings such as benzocyclohexyl and benzocyclopentyl; substituted multiplerings which are derivatives from the Diels-Alder of dicyclopentadiene;and arenes such as 9-fluorenyl.

Typical compounds represented by Formula II and the correspondinginitiators used to make these compounds include those listed bystructure in Table 2.

                                      TABLE 2                                     __________________________________________________________________________    Ex.                                                                           # Initiator              Product                                              __________________________________________________________________________       ##STR13##                                                                                            ##STR14##                                                                    wherein each z is from 1 to 26.                      __________________________________________________________________________

The compounds of Formula II each have a weight average molecular weightof at least 600. Preferably, the weight average molecular weight is fromabout 800 to about 4000, even more preferably from about 800 to about2000.

PREPARATION OF COMPOUNDS

The compounds of Formula I are illustratively prepared by alkoxylation,i.e., reacting an initiator selected from hydantoin and hydantoinalcohols with one or more epoxides in the presence of a potassiumcompound.

In one embodiment, the compounds of Formula I are prepared utilizingepoxides and hydantoin initiators represented by Formula XII: ##STR15##wherein R₂ and R₃ are as defined hereinbefore and R₂₂ is selected fromthe group consisting of hydrogen, hydrocarbyl, as defined hereinbefore,of 1 to 100 carbon atoms and substituted hydrocarbyl, as definedhereinbefore, of 1 to 100 carbon atoms. Non-limiting examples ofhydantoin initiators which are employed to prepare the compounds of thepresent invention include: 4-methylhydantoin, 5,5'-dimethylhydantoin,5-methyl-5-ethylhydantoin and 5-phenylhydantoin, with5,5'-dimethylhydantoin being the most preferred. Select hydantoininitiators of Formula XII are also available commercially, such as,Hydantoin (available commercially from Chemical Dynamics Corp. and alsoavailable commercially from Penta Manufacturing Company) and5,5'-dimethyl-hydantoin (available commercially from Chemical DynamicsCorp.).

The hydantoin initiators utilized can also be prepared using any of themethods known and described in the art, for example in U.S. Pat. No.4,209,608, incorporated herein by reference. In U.S. Pat. No. 4,209,608hydantoin initiators such as those represented by Formula XII in whichR₂₂ is hydrogen are formed by reacting a given ketone or aldehyde,sodium cyanide and ammonium carbonate. Those of ordinary skill in theart will recognize that known procedures may be used to substitutehydrocarbyls or substituted hydrocarbyls for the hydrogen of R₂₂.

In an alternative embodiment, the compounds of Formula I are preparedutilizing epoxides and hydantoin alcohol initiators represented bygeneral Formula XIII: ##STR16## wherein R₂ and R₃ are as definedhereinbefore, R₂₃ is selected from the group consisting of hydrogen,hydrocarbyl of 1 to 100 carbon atoms and substituted hydrocarbyl of 1 to100 carbon atoms and R₂₄ is selected from hydrocarbyl of 2 to 100 carbonatoms and substituted hydrocarbyl of 2 to 100 carbon atoms. Non-limitingexamples of hydantoin alcohol initiators which can be employed include5,5-dimethyl-hydantoin(2)-ethanol, 4-methyl-hydantoin(2)-ethanol and5-methyl-5-ethylhydantoin (2)-ethanol, with5,5-dimethyl-hydantoin(2)-ethanol being the most preferred.

The hydantoin alcohol initiators utilized can also be prepared by any ofthe methods known and described in the art, for example in U.S. Pat. No.3,907,719, incorporated herein by reference.

The compounds of Formula II are illustratively prepared by alkoxylation,i.e., reacting an initiator selected from bis-hydantoins and hydantoinalcohols with one or more epoxides in the presence of a potassiumcompound.

In one embodiment, the compounds of Formula II are prepared utilizingepoxides and bis-hydantoin initiators represented by Formula XIV:##STR17## wherein R₂, R₃, R₅, R₈ and R₉ are as defined hereinbefore.R₂₅, R₂₆ and R₂₇ are each independently selected from hydrogen,hydrocarbyl, as defined hereinbefore, of 1 to 100 carbon atoms andsubstituted hydrocarbyl, as defined hereinbefore, of 1 to 100 carbonatoms with the proviso that when R₂₂ and R₂₇ are hydrocarbyl orsubstituted hydrocarbyl, R₂₆ must be hydrogen. Non-limiting examples ofbis-hydantoin initiators which are employedinclude1,1'-methylenebis-(5-ethyl-5-methyl)-hydantoin,1,1-methylene-bis(5,5-dimethyl)-hydantoin,1,2-ethylene-bis(5,5-dimethyl)-hydantoin and1,1'-propylene-bis-(5-ethyl-5-methyl)-hydantoin,1,1-propylene-bis(5,5-dimethyl)-hydantoin.

The bis-hydantoin initiators utilized can also be prepared by any of themethods known and described in the art, for example in U.S. Pat. No.4,209,608, incorporated herein by reference. For example, in U.S. Pat.No. 4,209,608, bis-hydantoin initiators are formed by reacting a givenketone or aldehyde, sodium cyanide and ammonium carbonate to form anintermediate hydantoin of Formula XV or Formula XVI: ##STR18## whereinR₂, R₃, R₈ and R₉ are as defined hereinbefore. Two moles of theintermediate hydantoins (one mole each) is then condensed withformaldehyde under acidic conditions in the presence of a metal halidecatalyst if necessary to produce a bis-hydantoin initiator wherein R₅ isa methylene. Those of ordinary skill in the art will recognize thatknown procedures may be used to substitute hydrocarbyls or substitutedhydrocarbyls for the hydrogens in positions R₂₅ and R₂₇ .

Bis-hydantoins of Formula XIV wherein R₅ is an alkylene group whichcontains more than one carbon atom may be prepared by condensing twomoles of the intermediate hydantoin of Formulas XV and XVI with abis-acetal of Formula XVII: ##STR19## wherein n is 1 to 5, underanhydrous conditions followed by hydrogenation of the unsaturatedintermediate.

In an alternative embodiment, the compounds of Formula II are preparedutilizing epoxides and hydantoin alcohol initiators represented by thegeneral formula: ##STR20## wherein R₂, R₃, R₅, R₈ and R₉ are as definedhereinbefore, R₂₈ and R₃₀ are selected from the group consisting ofhydrogen, hydrocarbyl, as defined hereinbefore, of 1 to 100 carbon atomsand substituted hydrocarbyl, as defined hereinbefore, of 1 to 100 carbonatoms and R₂₉ is selected from the group consisting of hydrogen andhydroxyalkyl of the formula:

    --R.sub.31 OH                                              (XIX)

wherein R₃₁ is selected from the group consisting of alkyl of 1 to 20carbon atoms. Non-limiting examples of hydantoin alcohol initiatorswhich can be employed include1,3-bis(5',5'-dimethyl-hydantoinyl-3')-propan-2-ol, 1,3-bis(5,5'-pentamethylene-hydantoinyl-3')-propan-2-ol and1,3-bis(5,5'-tetramethylene-hydantoinyl-3)-propan-2-ol, with1,3-bis(5,5'-dimethylhydantoinyl-3')-propan-2-ol being the mostpreferred.

The bis-hydantoin alcohol initiators utilized can also be prepared byany of the methods known and described in the art, for example in U.S.Pat. No. 3,907,719 and U.S. Pat. No. 3,821,243, each incorporated hereinby reference. For example, in U.S. Pat. No. 3,907,719, an intermediatehydantoin of the formula: ##STR21## wherein R₂, R₃, R₅, R₈, R₉, R₂₅ andR₂₇ are as defined hereinbefore, is formed by reacting a given ketone,sodium cyanide and ammonium carbonate. Two moles of the intermediatehydantoin are then reacted with one mole of glycerin dichlorohydrin(1,3-dichloropropan-2-ol) in the presence of potassium carbonate anddimethylformamide to form the bis-hydantoin alcohol initiator of FormulaXVIII.

The one or more epoxides employed in the reaction with the initiators toprepare the compounds of Formula I and Formula II contain from 2 to 100carbon atoms, preferably from 2 to 50 carbon atoms, more preferably from2 to 20 carbon atoms, even more preferably from 2 to 4 carbon atoms, andmost preferably from 4 carbon atoms. The epoxides may be internalepoxides such as 2,3 epoxides of the formula: ##STR22## wherein R₃₂ andR₃₃ are selected from the group consisting of hydrogen, hydrocarbyl, asdefined hereinbefore, of 1 to 98 carbon atoms and substitutedhydrocarbyl, as defined hereinbefore, of 1 to 98 carbon atoms orterminal epoxides such as 1,2 epoxides of the formula: ##STR23## whereinR₃₂ and R₃₄ are selected from the group consisting of hydrogen,hydrocarbyl, as defined hereinbefore, or 1 to 98 carbon atoms andsubstituted hydrocarbyl, as defined hereinbefore, of 1 to 98 carbonatoms. (Note that Formulas XXII and XXIII correspond to geminal andvicinal hydrocarbyls as represented by Formulas V and VI for R₁₁ inFormula I; Formulas VII and VIII for R₄ in Formula I; and Formulas X andXI for R₁, R₇ and R₁₀ in Formula II). In both Formulas XXII and XXIII,R₃₂ and R₃₃, or alternatively R₃₂ and R₃₄, may be taken together to forma cycloalkylene epoxide or a vinylidene epoxide by forming a divalentlinking hydrocarbyl group of 3 to 12 carbon atoms.

When R₃₂, R₃₃ and/or R₃₄ are oxy-substituted hydrocarbyl, suitablecompounds of Formulas XXII and XXIII will include compounds such asnonylphenyl glycidyl ether, phenyl glycidyl ether, cresyl glycidylether, butyl glycidyl ether, alkyl C₁₂ -C₁₃ glycidyl ether, alkyl C₈-C₁₀ glycidyl ether, 2-ethylhexyl glycidyl ether and isopropyl glycidylether.

In the preferred embodiment, the terminal epoxides represented byFormula XXIII are utilized. Ideally these terminal epoxides are1,2-epoxyalkanes. Suitable 1,2-epoxyalkanes include 1,2-epoxyethane,1,2-epoxypropane, 1,2-epoxybutane, 1,2-epoxydecane, 1,2-epoxydodecane,1,2-epoxyhexadecane, 1,2-epoxyoctadecane and mixtures thereof.

In a typical preparation of Formula I compounds and Formula IIcompounds, the one or more epoxides and initiator are contacted at aratio from about 7:1 to about 55:1 moles of epoxide per mole ofinitiator. Preferably, they are contacted at a molar ratio from about10:1 to about 30:1, with the most preferred molar ratio being about20:1.

The reaction is carried out in the presence of potassium compounds whichact as alkoxylation catalysts. Such catalysts are conventional andinclude potassium methoxide, potassium ethoxide, potassium hydroxide,potassium hydride and potassium-t-butoxide. The preferred catalysts arepotassium hydroxide and potassium-t-butoxide. The catalysts are used ina base stable solvent such as alcohol, ether or hydrocarbons. Thecatalysts are employed in a wide variety of concentrations. Generally,the potassium compounds will be used in an amount from about 0.02% toabout 5.0% of the total weight of the mixture, preferably from about0.1% to about 2.0% of the total weight of the mixture, and mostpreferably about 0.2% of the total weight of the mixture.

The reaction is conveniently carried out in a conventional autoclavereactor equipped with heating and cooling means. The process ispracticed batchwise, continuously or semicontinuously.

The manner in which the alkoxylation reaction is conducted is notcritical to the invention. Illustratively, the initiator and potassiumcompound are mixed and heated under vacuum for a period of at least 30minutes. The one or more epoxides are then added to the resultingmixture, the reactor sealed and pressurized with nitrogen, and themixture stirred while the temperature is gradually increased.

The temperature for alkoxylation is from about 80° C. to about 250° C.,preferably from about 100° C. to about 150° C., and even more preferablyfrom about 120° C. to about 140° C. The alkoxylation reaction time isgenerally from about 2 to about 20 hours, although longer or shortertimes are employed.

Alkoxylation processes of the above type are known and are described,for example in U.S. Pat. No. 4,973,414, U.S. Pat. No. 4,883,826, U.S.Pat. No. 5,123,932 and U.S. Pat. No. 4,612,335, each incorporated hereinby reference.

The product of Formula I and Formula II is normally liquid and isrecovered by conventional techniques such as filtration anddistillation. The product is used in its crude state or is purified, ifdesired, by conventional techniques such as aqueous extraction, solidabsorption and/or vacuum distillation to remove any remainingimpurities.

Other methods for making the compounds of Formula I and Formula II areknown by those skilled in the art. For example, the compounds of FormulaI and Formula II are prepared by reacting an initiator as describedhereinbefore with other cyclic ethers. In addition, other catalystchemistry, such as the use of acidic catalysts, can be employed toachieve the compounds of Formula I and Formula II.

Fuel Compositions

The compounds of Formula I and Formula II are useful as additives infuel compositions which are burned or combusted in internal combustionengines. The fuel compositions of the present invention comprise a majoramount of a mixture of hydrocarbons in the gasoline boiling range and aminor amount of one or more of the compounds of Formula I, Formula II ormixtures thereof. As used herein, the term "minor amount" means lessthan about 10% by weight of the total fuel composition, preferably lessthan about 1% by weight of the total fuel composition and morepreferably less than about 0.1% by weight of the total fuel composition.

Suitable liquid hydrocarbon fuels of the gasoline boiling range aremixtures of hydrocarbons having a boiling range of from about 25° C. toabout 232° C. and comprise mixtures of saturated hydrocarbons, olefinichydrocarbons and aromatic hydrocarbons. Preferred are gasoline mixtureshaving a saturated hydrocarbon content ranging from about 40% to about80% by volume, an olefinic hydrocarbon content from 0% to about 30% byvolume and an aromatic hydrocarbon content from about 10% to about 60%by volume. The base fuel is derived from straight run gasoline, polymergasoline, natural gasoline, dimer and trimerized olefins, syntheticallyproduced aromatic hydrocarbon mixtures, or from catalytically cracked orthermally cracked petroleum stocks, and mixtures of these. Thehydrocarbon composition and octane level of the base fuel are notcritical. The octane level, (R+M)/2, will generally be above about 85.

Any conventional motor fuel base can be employed in the practice of thepresent invention. For example, hydrocarbons in the gasoline can bereplaced by up to a substantial amount of conventional alcohols orethers, conventionally known for use in fuels. The base fuels aredesirably substantially free of water since water could impede a smoothcombustion.

Normally, the hydrocarbon fuel mixtures to which the invention isapplied are substantially lead-free, but may contain minor amounts ofblending agents such as methanol, ethanol, ethyl tertiary butyl ether,methyl tertiary butyl ether, and the like, at from about 0.1% by volumeto about 15% by volume of the base fuel, although larger amounts may beutilized. The fuels can also contain conventional additives includingantioxidants such as phenolics, e.g., 2,6-di-tert-butylphenol orphenylenediamines, e.g., N,N'-di-sec-butyl-p-phenylenediamine, dyes,metal deactivators, dehazers such as polyester-type ethoxylatedalkylphenol-formaldehyde resins. Corrosion inhibitors, such as apolyhydric alcohol ester of a succinic acid derivative having on atleast one of -its alpha-carbon atoms an unsubstituted or substitutedaliphatic hydrocarbon group having from 20 to 500 carbon atoms, forexample, pentaerythritol diester of polyisobutylene-substituted succinicacid, the polyisobutylene group having an average molecular weight ofabout 950, in an amount from about 1 ppm by weight to about 1000 ppm byweight, may also be present. The fuels can also contain antiknockcompounds such as methyl cyclopentadienylmanganese tricarbonyl andortho-azidophenol as well as co-antiknock compounds such as benzoylacetone.

An effective amount of one or more compounds of Formula I and/or FormulaII is introduced into the combustion zone of the engine in a variety ofways to prevent build-up of deposits, or to accomplish the reduction ofintake valve deposits or the modification of existing deposits that arerelated to octane requirement. As mentioned, a preferred method is toadd a minor amount of one or more compounds of Formula I and/or FormulaII to the fuel. For example, one or more compounds of Formula I and/orFormula II are added directly to the fuel or are blended with one ormore carriers and/or one or more additional detergents to form anadditive concentrate. The additive concentrate can be added to the fuelat a later time.

The amount of hydantoin-containing polyether alcohol used will depend onthe particular variation of Formula I and/or Formula II used, theengine, the fuel, and the presence or absence of carriers and additionaldetergents. Generally, each compound of Formula I and/or Formula II isadded in an amount up to about 1000 ppm by weight, especially from about1 ppm by weight to about 600 ppm by weight based on the total weight ofthe fuel composition. Preferably, the amount will be from about 50 ppmby weight to about 400 ppm by weight, and even more preferably fromabout 75 ppm by weight to about 250 ppm by weight based on the totalweight of the fuel composition.

The carrier, when utilized, will have a weight average molecular weightfrom about 500 to about 5000. Suitable carriers, when utilized, includehydrocarbon based materials such as polyisobutylenes (PIB's),polypropylenes (PP's) and polyalphaolefins (PAO's); polyether basedmaterials such as polybutylene oxides. (poly BO's), polypropylene oxides(poly PO's), polyhexadecene oxides (poly HO's) and mixtures thereof(i.e., both (poly BO)+(poly PO) and (poly-BO-PO)); and mineral oils suchas Exxon Naphthenic 900 sus and high viscosity index (HVI) oils. Thecarrier is preferably selected from PIB's, poly BO's, and poly PO's,with poly BO's being the most preferred.

The carrier concentration in the final fuel composition is up to about1000 ppm by weight. When a carrier is present, the preferredconcentration is from about 50 ppm by weight to about 400 ppm by weight,based on the total weight of the fuel composition. Once the carrier isblended with one or more compounds of Formula I and/or Formula II, theblend is added directly to the fuel or packaged for future use.

The fuel compositions of the present invention may also contain one ormore additional detergents. When additional detergents are utilized, thefuel composition will comprise a mixture of a major amount ofhydrocarbons in the gasoline boiling range as described hereinbefore, aminor amount of one or more compounds of Formula I and/or Formula II asdescribed hereinbefore and a minor amount of an additional detergentselected from polyalkylenyl amines, Mannich amines, polyalkenylsuccinimides, poly(oxyalkylene) carbamates, poly(alkenyl)-N-substitutedcarbamates and mixtures thereof. As noted above, a carrier as describedhereinbefore may also be included. As used herein, the term "minoramount" means less than about 10% by weight of the total fuelcomposition, preferably less than about 1% by weight of the total fuelcomposition and more preferably less than about 0.1% by weight of thetotal fuel composition.

The polyalkylenyl amine detergents utilized comprise at least onemonovalent hydrocarbon group having at least 50 carbon atoms and atleast one monovalent hydrocarbon group having at most five carbon atomsbound directly to separate nitrogen atoms of a diamine. Preferredpolyalkylenyl amines are polyisobutenyl amines. Polyisobutenyl aminesare known in the art and representative examples are disclosed invarious U.S. Patents including U.S. Pat. No. 3,753,670, U.S. Pat. No.3,756,793, U.S. Pat. No. 3,574,576 and U.S. Pat. No. 3,438,757, eachincorporated herein by reference. Particularly preferred polyisobutenylamines for use in the present fuel composition includeN-polyisobutenyl-N',N'-dimethyl-1,3-diaminopropane (PIB-DAP) and OGA-472(a polyisobutenyl ethylene diamine available commercially from Oronite).

The Mannich amine detergents utilized comprise a condensation product ofa high molecular weight alkyl-substituted hydroxyaromatic compound, anamine which contains an amino group having at least one active hydrogenatom (preferably a polyamine), and an aldehyde. Such Mannich amines areknown in the art and are disclosed in U.S. Pat. No. 4,231,759,incorporated herein by reference. Preferably, the Mannich amine is analkyl substituted Mannich amine.

The polyalkenyl succinimide detergents comprise the reaction product ofa dibasic acid anhydride with either a polyoxyalkylene diamine, ahydrocarbyl polyamine or mixtures of both. Typically the succinmide issubstituted with the polyalkenyl group but the polyalkenyl group may befound on the polyoxyalkylene diamine or the hydrocarbyl polyamine.Polyalkenyl succinimides are also known in the art and representativeexamples are disclosed in various U.S. Patents including U.S. Pat. No.4,810,261, U.S. Pat. No. 4,852,993, U.S. Pat. No. 4,968,321, U.S. Pat.No. 4,985,047, U.S. Pat. No. 5,061,291 and U.S. Pat. No. 5,147,414, eachincorporated herein by reference.

The poly(oxyalkylene) carbamate detergents comprise an amine moiety anda poly(oxyalkylene) moiety linked together through a carbamate linkage,i.e.,

    --O--C(O)--N--                                             (XXIV)

These poly(oxyalkylene) carbamates are known in the art andrepresentative examples are disclosed in various U.S. Patents including,U.S. Pat. No. 4,191,537, U.S. Pat. No. 4,160,648, U.S. Pat. No.4,236,020, U.S. Pat. No. 4,270,930, U.S. Pat. No. 4,288,612 and U.S.Pat. No. 4,881,945, each incorporated herein by reference. Particularlypreferred poly(oxyalkylene) carbamates for use in the present fuelcomposition include OGA-480 (a poly(oxyalkylene) carbamate which isavailable commercially from Oronite).

The poly(alkenyl)-N-substituted carbamate detergents utilized are of theformula: ##STR24## in which R is a poly(alkenyl) chain; R¹ is ahydrocarbyl or substituted hydrocarbyl group; and A is an N-substitutedamino group. Poly(alkenyl)-N-substituted carbamates are known in the artand are disclosed in U.S. Pat. No. 4,936,868, incorporated herein byreference.

The one or more additional detergents are added directly to thehydrocarbons, blended with one or more carriers, blended with one ormore compounds of Formula I and/or Formula II, or blended with one ormore compounds of Formula I and/or Formula II and one or more carriersbefore being added to the hydrocarbons.

The concentration of the one or more additional detergents in the finalfuel composition is generally up to about 1000 ppm by weight for eachadditional detergent. When one or more additional detergents areutilized, the preferred concentration for each additional detergent isfrom about 50 ppm by weight to about 400 ppm by weight, based on thetotal weight of the fuel composition, even more preferably from about 75ppm by weight to about 250 ppm by weight, based on the total weight ofthe fuel composition.

Engine Tests

Decreasing Intake Valve Deposits

The invention further provides a process for decreasing intake valvedeposits in engines utilizing the hydantoin-containing polyether alcoholcompounds of the present invention. The process comprises supplying toand combusting or burning in an internal combustion engine a fuelcomposition comprising a major amount of hydrocarbons in the gasolineboiling range and a minor amount of one or more compounds of Formula Iand/or Formula II as described hereinbefore.

By supplying to and combusting or burning the fuel composition in aninternal combustion engine, deposits in the induction system,particularly deposits on the tulips of the intake valves, are reduced.The reduction is determined by running an engine with clean inductionsystem components and pre-weighed intake valves on dynamometer teststands in such a way as to simulate road operation using a variety ofcycles at varying speeds while carefully controlling specific operatingparameters. The tests are run for a specific period of time on the fuelcomposition to be tested. Upon completion of the test, the inductionsystem deposits are visually rated, the valves are reweighed and theweight of the valve deposits is determined.

Controlling Octane Requirement Increases

The invention further provides a process for controlling octanerequirement increases in engines utilizing the hydantoin-containingpolyether alcohols of the present invention. The process comprisessupplying to and combusting or burning in an internal combustion enginea fuel composition comprising a major amount of hydrocarbons in thegasoline boiling range and a minor amount of one or more compounds ofFormula I and/or Formula II as described hereinbefore.

Octane requirement is the maximum octane number of a gasoline thatpresents trace knock in a given engine within the engine's normaloperating range. An increase in octane requirement is generallyexperienced during mileage accumulation on a new engine. The increase istypically attributed to an increase in engine deposits. Octanerequirement increase control is a performance feature that is usuallyexpressed as a comparison of the octane requirement increase developedwith a gasoline containing additives (test gasoline) relative to aversion of the same gasoline without additives (base gasoline), i.e.,the positive difference obtained by subtracting the results of gasolinecontaining additives from gasoline which does not contain additives.

The test protocol for octane requirement increase control must establishthe stable octane requirement of the base gasoline relative to a cleanengine. Base gasoline is typically the test gasoline without additivesor special treatment; however, it may be gasoline containing additivesfor a specific comparison.

Octane requirement increase control testing consists of operating anengine assembled with clean combustion chambers and induction systemcomponents on a test gasoline to octane stabilization, measuring theoctane requirement at regular intervals. The octane requirement increasecontrol is the difference between the stabilized octane requirement ofthe engine operated on test gasoline and that of the stabilized octanerequirement of the engine on base gasoline.

Reduction of Octane Requirement

The invention still further provides a process for reducing octanerequirement in engines utilizing the hydantoin-containing polyetheralcohols of the present invention. The process comprises supplying toand combusting or burning in an internal combustion engine a fuelcomposition comprising a major amount of hydrocarbons in the gasolineboiling range and a minor amount of one or more compounds of Formula Iand/or Formula II as described hereinbefore.

Octane requirement reduction is the reduction of the octane requirementof an engine by the action of a particular gasoline, usually measured asa decrease from a stabilized octane requirement condition.

Octane requirement reduction is a performance feature that demonstratesa reduction from the established octane requirement of a base gasolinein a given engine. Octane requirement reduction testing consists ofoperating an engine, which has achieved stable octane requirement usingbase gasoline, on a test gasoline for approximately 100 hours. Octanemeasurements are made daily and octane requirement reduction is areduction of octane requirement from that of base gasoline. Severaloctane requirement reduction tests may be conducted in a series for fuelto fuel comparison, or test fuel to base fuel comparison, byrestabilizing on base fuel between octane requirement reduction tests.

The contribution of specific deposits is determined by removing depositsof interest and remeasuring octane requirement immediately after theengine is warmed to operating temperature. The octane requirementcontribution of the deposit is the difference in ratings before andafter deposit removal.

The ranges and limitations provided in the instant specification andclaims are those which are believed to particularly point out anddistinctly claim the instant invention. It is, however, understood thatother ranges and limitations that perform substantially the samefunction in substantially the same way to obtain the same orsubstantially the same result are intended to be within the scope of theinstant invention as defined by the instant specification and claims.

The invention will be described by the following examples which areprovided for illustrative purposes and are not to be construed aslimiting the invention.

EXAMPLES

Compound Preparation

The hydantoin-containing polyether alcohol compounds used in thefollowing examples were prepared by reacting an initiator with epoxidesin the presence of a potassium compound to produce compounds of FormulaI and/or Formula II having a weight average molecular weight (MW) fromabout 600 to about 4000 as measured by gel permeation chromatography(GPC). Rotary evaporation under reduced pressure typically was conductedat a temperature from room temperature to 120° C.

Example 1 (FORMULA I)

Step 1-Preparation of Initiator

A mixture of 5,5-dimethyl hydantoin (128 g, 1.0 mole), ethylenecarbonate (88 g, 1 mole) and potassium fluoride (0.0017 mole) was placedinto a three-necked round-bottomed flask equipped with a heating mantle,mechanical stirrer, nitrogen inlet-outlet line, thermometer andDean-Stark Trap. The mixture was heated to 150° C. for 6hours. Theprogress of the reaction was monitored by the release of CO₂by-products. After the reaction was completed, the product was cooled toroom temperature. The product obtained,5,5dimethyl-hydantoin(2)-ethanol, was used without further purification.

Step 2-Butoxylation of Initiator

A mixture of the initiator of Step 1 (5,5-dimethyl-hydantoin(2)-ethanol,43 g, 0.25 moles), toluene (15 g) potassium tert-butoxide (0.4 g) wassubjected to rotary evaporation under reduced pressure. The resultingproduct was charged along with 1,2-epoxybutane (457 g, 6.3 moles) into aone liter autoclave reactor equipped with a heating device, temperaturecontroller, mechanical stirrer and water cooling system. The autoclavereactor was sealed, purged of air with nitrogen and then pressurized to50 psi with nitrogen at room temperature. The mixture was then heated toa temperature of 137° C.-147° C. for 5.5 hours. The autoclave reactorwas then cooled to room temperature and excess gas was vented. A finalproduct (493 g of a clear, transparent, light-colored liquid) wasobtained after rotary evaporation under reduced pressure, waterextraction and rotary evaporation was repeated. GPC analysis showedMW=1390 and a polydispersity of 1.09. The final product contained twobutylene oxide backbones.

Example 2 (FORMULA II)

Step 1-Preparation of Initiator

In a three liter round bottom flask equipped with a mechanical stirrer,thermometer and reflux condenser, a mixture of 5,5 dimethyl hydantoin(512 g, 4.0 moles), epichlorohydrin (92.5 g, 2.2 moles), sodiumhydroxide (8.8 g, 2.2 moles), ethanol (512 g) and water (322 g) washeated to reflux for six hours. Following the reaction, sodium chloridewas filtered off while the mixture was at a temperature of 60° C.-70° C.The filtrate was evaporated to dryness and the residue wasrecrystallized from water to give 378 g of 1,3-bis (5,5'-dimethylhydantoinyl-3')-propan-2-ol with a melting point of 189°-190° C.

Step 2-Butoxylation of Initiator

The initiator of Step 1 (1,3-bis (5,5'-dimethylhydantoinyl-3')-propan-2-ol, 58 g, 0.19 moles), 1,2-epoxybutane (242 g,3.4 moles), potassium tert-butoxide (1.7 g) and toluene (100 g) wascharged directly into a one liter autoclave reactor equipped with aheating device, temperature controller, mechanical stirrer and watercooling system. The autoclave reactor was sealed, purged of air withnitrogen and then pressurized to 50 psi with nitrogen at roomtemperature. The mixture was then heated to a temperature of 132° C-142°C. for 10 hours. The autoclave reactor was then cooled to roomtemperature and excess gas was vented. The crude product was subjectedto rotary evaporation under reduced pressure, extracted with water andthen subjected to rotary evaporation again to remove impurities. A finallight-yellow transparent liquid product (240 g) was obtained. GPCanalysis showed MW=1200 and a polydispersity of 1.05.

Example 3 (FORMULA II)

The initiator produced in Step 1 of Example 2 (1,3-bis (5,5'-dimethylhydantoinyl-3')-propan-2-ol, 62 g, 0.20 mole), 1,2-epoxybutane (438 g,6.1 moles), potassium tert-butoxide (2.9 g) and toluene (50 g) wascharged directly into a one liter autoclave reactor equipped with aheating device, temperature controller, mechanical stirrer and watercooling system. The autoclave reactor was sealed, purged of air withnitrogen and then pressurized to 50 psi with nitrogen at roomtemperature. The mixture was heated to a temperature of 137° C.-142° C.for seven hours. The autoclave reactor was then cooled to roomtemperature and excess gas was vented. The crude product was subjectedto rotary evaporation under reduced pressure, extracted with water andthen subjected to rotary evaporation again. A light brown liquid product(447 g) having a higher molecular weight that of Example 2 was obtained.GPC analysis indicated MW=1730 and a polydispersity of 1.08. The hydroxynumber showed 76 mg KOH/g indicating an average of three hydroxy poly1,2-epoxybutane chains.

Example 4 (FORMULA I)

1-methyl hydantoin (21.4 g, 0.19 moles), 1,2-epoxybutane (280 g, 3.9moles), potassium tert-butoxide 43.4 g) and toluene (100 g) was directlycharged into a one liter autoclave reactor equipped with a heatingdevice, temperature controller, mechanical stirrer and water coolingsystem. The autoclave reactor was sealed, purged of air with nitrogenand then pressurized to 50 psi with nitrogen at room temperature. Themixture was heated to a temperature of 129° C.-160° C. for six hours.The autoclave reactor was then cooled to room temperature and excess gaswas vented. The crude product was subjected to rotary evaporation underreduced pressure, extracted with water and then subjected to rotaryevaporation again. A brown liquid final product (270 g) was obtained.GPC analysis indicated MW=1060 and a polydispersity of 2.03.

Test Results

In each of the following tests, the base fuel utilized comprised eitherpremium unleaded gasoline (PU) (90±octane, R+M/2!) and/or regularunleaded gasoline (RU) (85-88 octane, R+M/2!). Those skilled in the artwill recognize that fuels containing heavy catalytically cracked stocks,such as most regular fuels, are typically more difficult to additize inorder to control deposits and effectuate octane requirement reductionand octane requirement increase control. The hydantoin-containingpolyether alcohol compounds utilized were prepared as indicated byExample number and were used at the concentration indicated in ppm byweight. The tests employed are described below and the results of thevarious tests are set forth in the tables below.

Intake Valve Deposit Tests

Engines from vehicles were installed in dynamometer cells in such a wayas to simulate road operation using a cycle of idle, low speed and highspeed components while carefully controlling specific operatingparameters. Fuels with and without the compounds of Formula I andFormula II were tested in a variety of engines having port fuelinjection including, 3.0 L Fords (FORD), 2.3 L Oldsmobiles (OLDS) and3.1 L Chevrolets (CHEV) to determine the effectiveness of the instantcompounds in reducing intake valve deposits ("L" refers to liter).Carbureted 0.359 L Honda generator engines were also utilized todetermine the effectiveness of the instant compounds in reducing intakevalve deposits.

Before each test, the engine was inspected, the induction systemcomponents were cleaned and new intake valves were weighed andinstalled. The oil was changed and new oil and fuel filters, gaskets andspark plugs were installed.

In all engines except the Honda, the tests were run in cycles consistingof idle, 35 mph and 65 mph for a period of 100 hours unless indicatedotherwise. In the Honda engines, the tests were run in cycles consistingof a no load idle mode for one minute followed by a three minute modewith a load at 2200 rpm's for a period of 40 hours unless indicatedotherwise. At the end of each test, the intake valves were removed andweighed.

Tables 3 and 4 include data obtained using compounds of the presentinvention (Formula I and Formula II). All tests of compounds of thepresent invention were carried out with additive concentrations (theamount of Compound Example # used) of 200 parts per million (ppm)non-volatile matter (nvm). Base Fuel results which have 0 ppm additiveare also included for comparison purposes. The base fuels are indicatedby the absence of a Compound Example # (indicated in the CompoundExample # column by --).

                  TABLE 3                                                         ______________________________________                                        Intake Valve Deposits in Honda Generator Engines                              Compound        Concentration                                                                             Engine                                                                              Average Deposit                             Example #                                                                              Fuel   ppm By Wt.  #     Weight (mg)                                 ______________________________________                                        2        PU     200         H3C   11.7                                        --       "      0           *     33.2                                        3        PU     200         H3C   13.3                                        --       "      0           *     33.2                                        4        RU     200         H2C   35.8                                        --       "      0           **    45.9                                        2        RU     200         H3C   48.1                                        --       "      0           ***   88.1                                        ______________________________________                                         -- Indicates the results achieved with base fuel in the absence of any        additive compound (0 ppm additive compound).                                  *Average of 4 test runs using the same base fuel in other Honda Generator     Engines.                                                                      **Average of 4 test runs using the same base fuel in other Honda Generato     Engines.                                                                      ***Average of 2 test runs in the same base fuel in other Honda Generator      Engines.                                                                 

                  TABLE 4                                                         ______________________________________                                        Intake Valve Deposits in Various Engines                                      Compound                  Concentration                                                                           Avg. Deposit                              Example #                                                                              Engine   Fuel    ppm By Wt.                                                                              Wt (mg)                                   ______________________________________                                        1        3.0 L    RU      200       232.0                                              FORD                                                                 --       3.0 L    "       0         359.8                                              FORD                                                                 1        2.3 L    RU      200       147.9                                              OLDS                                                                 --       3.0 L    "       0         141.0                                              OLDS                                                                 1        3.1 L    PU      200       147.1                                              CHEV                                                                 --       3.1 L    "       0         72.2                                               CHEV                                                                 ______________________________________                                         -- Indicates the results achieved with base fuel in the absence of any        additive compound (0 ppm additive compound).                             

What is claimed is:
 1. A fuel composition comprising a mixture of amajor amount of hydrocarbons in the gasoline boiling range and a minoramount of an additive compound having the formula: ##STR25## wherein R₁is selected from the group consisting of hydrocarbyl of 1 to 100 carbonatoms, substituted hydrocarbyl of 1 to 100 carbon atoms andpolyoxyalkylene alcohol of 2 to 200 carbon atoms; R₂ and R₃ are eachindependently selected from the group consisting of hydrogen,hydrocarbyl of 1 to 100 carbon atoms and substituted hydrocarbyl of 1 to100 carbon or R₂ and R₃ taken together with the carbon atom to whichthey are connected form a cyclic group of 4 to 100 carbon atoms; each R₄is independently selected from the group consisting of hydrocarbyl of 2to 100 carbon atoms and substituted hydrocarbyl of 2 to 100 carbonatoms; x is from 1 to 50; and the weight average molecular weight of theadditive compound is at least about
 600. 2. The fuel composition ofclaim 1 wherein said additive compound is present in an amount fromabout 50 ppm by weight to about 400 ppm by weight based on the totalweight of the fuel composition.
 3. The fuel composition of claim 2wherein the weight average molecular weight of the additive compound isfrom about 800 to about
 4000. 4. The fuel composition of claim 3 whereineach R₄ is independently selected from hydrocarbyl of 2 to 50 carbonatoms and substituted hydrocarbyl of 2 to 50 carbon atoms.
 5. The fuelcomposition of claim 4 wherein R₄ is hydrocarbyl of the formula:##STR26## wherein each R₁₇ is independently selected from hydrogen,hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to18 carbon atoms and each R₁₅ is independently selected from hydrogen,hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to18 carbon atoms.
 6. The fuel composition of claim 5 wherein R₂ and R₃are each independently selected from the group consisting of hydrogenand hydrocarbyl of 1 to 20 carbon atoms.
 7. The fuel composition ofclaim 6 wherein R₁ is selected from the group consisting of hydrocarbylof 1 to 20 carbon atoms and substituted hydrocarbyl of 1 to 20 carbonatoms.
 8. The fuel composition of claim 7 wherein R₁ is alkyl of 1 to 20carbon atoms.
 9. The fuel composition of claim 8 wherein R₁ is alkyl of1 carbon atom, R₂ and R₃ are each hydrogen, each R₁₇ is hydrogen, eachR₁₅ is independently selected from hydrogen and alkyl of 1 to 2 carbonatoms and x is from 8 to
 26. 10. The fuel composition of claim 6 whereinR₁ is polyoxyalkylene of the formula:

    --(R.sub.11 --O).sub.y H

wherein each R₁₁ is independently selected from the group consisting ofhydrocarbyl of 2 to 100 carbon atoms and substituted hydrocarbyl of 2 to100 carbon atoms and y is from 1 to
 50. 11. The fuel composition ofclaim 10 wherein each R₁₁ is independently selected from the groupconsisting of hydrocarbyl of 2 to 50 carbon atoms and substitutedhydrocarbyl of 2 to 50 carbon atoms.
 12. The fuel composition of claim11 wherein R₁₁ is hydrocarbyl of the formula: ##STR27## wherein each R₁₄is independently selected from hydrogen, hydrocarbyl of 1 to 18 carbonatoms and substituted hydrocarbyl of 1 to 18 carbon atoms and each R₁₂is independently selected from hydrogen, substituted and hydrocarbyl of1 to 18 carbon atoms.
 13. The fuel composition of claim 12 wherein R₂and R₃ are each hydrogen, each R₁₄ is hydrogen, each R₁₂ isindependently selected from the group consisting of hydrogen and alkylof 1 to 2 carbon atoms, each R₁₇ is hydrogen, each R₁₅ is independentlyselected from hydrogen and alkyl of 1 to 2 carbon atoms, x is from 1 to26 and y is from 1 to
 26. 14. The fuel composition of claim 4 wherein R₄is hydrocarbyl of the formula: ##STR28## wherein each R₁₆ isindependently selected from the group consisting of hydrogen,hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to18 carbon atoms and each R₁₅ is independently selected from the groupconsisting of hydrogen, hydrocarbyl of 1 to 18 carbon atoms andsubstituted hydrocarbyl of 1 to 18 carbon atoms.
 15. The fuelcomposition of claim 10 wherein R₁₁ is hydrocarbyl of the formula:##STR29## wherein each R₁₃ is independently selected from the groupconsisting of hydrogen, hydrocarbyl of 1 to 18 carbon atoms andsubstituted hydrocarbyl of 1 to 18 carbon atoms and each R₁₂ isindependently selected from hydrogen, hydrocarbyl of 1 to 18 carbonatoms and substituted hydrocarbyl of 1 to 18 carbon atoms.
 16. A methodfor decreasing intake valve deposits in an internal combustion enginewhich comprises burning in said engine a fuel composition comprising amajor amount of hydrocarbons in the gasoline boiling range and a minoramount of an additive compound having the formula: ##STR30## wherein R₁is selected from the group consisting of hydrocarbyl of 1 to 100 carbonatoms, substituted hydrocarbyl of 1 to 100 carbon atoms andpolyoxyalkylene alcohol of 2 to 200 carbon atoms; R₂ and R₃ are eachindependently selected from the group consisting of hydrogen,hydrocarbyl of 1 to 100 carbon atoms and substituted hydrocarbyl of 1 to100 carbon or R₂ and R₃ taken together with the carbon atom to whichthey are connected form a cyclic group of 4 to 100 carbon atoms; each R₄is independently selected from the group consisting of hydrocarbyl of 2to 100 carbon atoms and substituted hydrocarbyl of 2 to 100 carbonatoms; x is from 1 to 50; and the weight average molecular weight of theadditive compound is at least about
 600. 17. The method of claim 16wherein said additive compound is present in an amount from about 50 ppmby weight to about 400 ppm by weight based on the total weight of thefuel composition.
 18. The method of claim 17 wherein the weight averagemolecular weight of the additive compound is from about 800 to about4000.
 19. The method of claim 18 wherein each R₄ is independentlyselected from hydrocarbyl of 2 to 50 carbon atoms and substitutedhydrocarbyl of 2 to 50 carbon atoms.
 20. The method of claim 19 whereinR₄ is hydrocarbyl of the formula: ##STR31## wherein each R₁₇ isindependently selected from hydrogen, hydrocarbyl of 1 to 18 carbonatoms and substituted hydrocarbyl of 1 to 18 carbon atoms and each R₁₅is independently selected from hydrogen, hydrocarbyl of 1 to 18 carbonatoms and substituted hydrocarbyl of 1 to 18 carbon atoms.
 21. Themethod of claim 20 wherein R₂ and R₃ are each independently selectedfrom the group consisting of hydrogen and hydrocarbyl of 1 to 20 carbonatoms.
 22. The method of claim 21 wherein R₁ is selected from the groupconsisting of hydrocarbyl of 1 to 20 carbon atoms and substitutedhydrocarbyl of 1 to 20 carbon atoms.
 23. The method of claim 22 whereinR₁ is alkyl of 1 to 20 carbon atoms.
 24. The method of claim 23 whereinR₁ is alkyl of 1 carbon atom, R₂ and R₃ are each hydrogen, each R₁₇ ishydrogen, each R₁₅ is independently selected from hydrogen and alkyl of1 to 2 carbon atoms and x is from 8 to
 26. 25. The method of claim 21wherein R₁ is polyoxyalkylene of the formula: ##STR32## wherein each R₁₁is independently selected from the group consisting of hydrocarbyl of 2to 100 carbon atoms and substituted hydrocarbyl of 2 to 100 carbon atomsand y is from 1 to
 50. 26. The method of claim 25 wherein each R₁₁ isindependently selected from the group consisting of hydrocarbyl of 2 to50 carbon atoms and substituted hydrocarbyl of 2 to 50 carbon atoms. 27.The method of claim 26 wherein R₁₁ is hydrocarbyl of the formula:##STR33## wherein each R₁₄ is independently selected from hydrogen,atoms and substituted hydrocarbyl of 1 to 18 carbon atoms and each R₁₂is independently selected from hydrogen, hydrocarbyl of 1 to 18 carbonatoms and substituted hydrocarbyl of 1 to 18 carbon atoms.
 28. Themethod of claim 27 wherein R₂ and R₃ are each hydrogen, each R₁₄ ishydrogen, each R₁₂ is independently selected from the group consistingof hydrogen and alkyl of 1 to 2 carbon atoms, each R₁₇ is hydrogen, eachR₁₅ is independently selected from hydrogen and alkyl of 1 to 2 carbonatoms, x is from 1 to 26 and y is from 1 to
 26. 29. The method of claim19 wherein R₄ is hydrocarbyl of the formula: ##STR34## wherein each R₁₆is independently selected from the group consisting of hydrogen,hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to18 carbon atoms and each R₁₅ is independently selected from the groupconsisting of hydrogen, hydrocarbyl of 1 to 18 carbon atoms andsubstituted hydrocarbyl of 1 to 18 carbon atoms.
 30. The method of claim25 wherein R₁₁ is hydrocarbyl of the formula: ##STR35## wherein each R₁₃is independently selected from the group consisting of hydrogen,hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to18 carbon atoms and each R₁₂ is independently selected from hydrogen,hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to18 carbon atoms.
 31. A method for reducing octane requirement in aninternal combustion engine which comprises burning in said engine a fuelcomposition comprising a major amount of hydrocarbons in the gasolineboiling range and a minor amount of an additive compound having theformula: ##STR36## wherein R₁ is selected from the group consisting ofhydrocarbyl of 1 to 100 carbon atoms, substituted hydrocarbyl of 1 to100 carbon atoms and polyoxyalkylene alcohol of 2 to 200 carbon atoms;R₂ and R₃ are each independently selected from the group consisting ofhydrogen, hydrocarbyl of 1 to 100 carbon atoms and substitutedhydrocarbyl of 1 to 100 carbon or R₂ and R₃ taken together with thecarbon atom to which they are connected form a cyclic group of 4 to 100carbon atoms; each R₄ is independently selected from the groupconsisting of hydrocarbyl of 2 to 100 carbon atoms and substitutedhydrocarbyl of 2 to 100 carbon atoms; x is from 1 to 50; and the weightaverage molecular weight of the additive compound is at least about 600.32. A method for controlling the octane requirement increase in aninternal combustion engine which comprises burning in said engine a fuelcomposition comprising a major amount of hydrocarbons in the gasolineboiling range and a minor amount of an additive compound having theformula: ##STR37## wherein R₁ is selected from the group consisting ofhydrocarbyl of 1 to 100 carbon atoms, substituted hydrocarbyl of 1 to100 carbon atoms and polyoxyalkylene alcohol of 2 to 200 carbon atoms;R₂ and R₃ are each independently selected from the group consisting ofhydrogen, hydrocarbyl of 1 to 100 carbon atoms and substitutedhydrocarbyl of 1 to 100 carbon or R₂ and R₃ taken together with thecarbon atom to which they are connected form a cyclic group of 4 to 100carbon atoms; each R₄ is independently selected from the groupconsisting of hydrocarbyl of 2 to 100 carbon atoms and substitutedhydrocarbyl of 2 to 100 carbon atoms; x is from 1 to 50; and the weightaverage molecular weight of the additive compound is at least about 600.33. A fuel composition comprising a mixture of:(a) a major amount ofhydrocarbons in the gasoline boiling range; (b) a minor amount of anadditive compound having the formula: ##STR38## wherein R₁ is selectedfrom the group consisting of hydrocarbyl of 1 to 100 carbon atoms,substituted hydrocarbyl of 1 to 100 carbon atoms and polyoxyalkylenealcohol of 2 to 200 carbon atoms; R₂ and R₃ are each independentlyselected from the group consisting of hydrogen, hydrocarbyl of 1 to 100carbon atoms and substituted hydrocarbyl of 1 to 100 carbon or R₂ and R₃taken together form a cyclic group of 4 to 100 carbon atoms; each R₄ isindependently selected from the group consisting of hydrocarbyl of 2 to100 carbon atoms and substituted hydrocarbyl of 2 to 100 carbon atoms; xis from 1 to 50; and the weight average molecular weight of the additivecompound is at least-about 600; and (c) a minor amount of a detergentselected from the group consisting of polyalkylenyl amines, mannichamines, polyalkenyl succinimides, poly(oxyalkylene) carbamates,poly(alkenyl)-N-substituted carbamates and mixtures thereof.